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Published April 1993 | public
Journal Article

Incorporation of phthalocyanines by cationic and anionic clays via ion exchange and direct synthesis

Abstract

Phthalocyanines (Pc) and metallophthalocyanines were incorporated into the galleries of anionic and cationic clays via ion exchange and in situ crystallization of the synthetic clay layers. Intercalation compounds between the layered magnesium silicate clay hectorite and cationic phthalocyanines were directly prepared by refluxing for 2 days aqueous solutions of silica sol, magnesium hydroxide, lithium fluoride, and either alcian blue dyes (Cu(II)Pc) or 15-crown-5 tetra-substituted phthalocyanine (15C5Pc). The CuPc dyes are tetrapositively charged through peripheral quaternary ammonium groups, whereas the 15C5Pc is electrically neutral. Anionic clays prepared by hydrolysis of mixed solutions of aluminum nitrate, magnesium nitrate, and copper(II) phthalocyaninetetrasulfonic acid, tetrasodium salt (CuPcTs) in sodium hydroxide resulted in crystallization of an intercalation compound between a layered double hydroxide (LDH) and this anionic Pc. The material prepared by ion exchange of CuPcTs into a wet, freshly prepared LDH was superior in crystallinity. The phthalocyanines are oriented parallel to cationic hectorite clay layers (gallery heights 4.5-6.5 Å) and perpendicular to anionic layered double hydroxide clay layers (gallery height 18.2 Å) in correlation with their hosts' respective layer charge densities.

Additional Information

© 1993 American Chemical Society. Received October 6, 1992. Revised Manuscript Received January 18, 1992. The helpful comments of J. W. White and the reviewers are greatly appreciated. The technical assistance of C. A. Pieper and P. L. Shaver, Jr. is acknowledged; partial funding for J.E.F., C. A. Pieper, and P. L. Shaver, Jr. was provided for by the Division of Educational Programs, ANL. The microanalysis performed at ANL was done by I. Fox. This work was performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, US. Department of Energy, under Contract No. W-31-109-ENG-38.

Additional details

Created:
August 20, 2023
Modified:
October 18, 2023